EP0245596A1 - Method for determining the J-value in the oxidative coupling reaction of phenols to polyphenylene ethers - Google Patents

Method for determining the J-value in the oxidative coupling reaction of phenols to polyphenylene ethers Download PDF

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EP0245596A1
EP0245596A1 EP87102799A EP87102799A EP0245596A1 EP 0245596 A1 EP0245596 A1 EP 0245596A1 EP 87102799 A EP87102799 A EP 87102799A EP 87102799 A EP87102799 A EP 87102799A EP 0245596 A1 EP0245596 A1 EP 0245596A1
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value
reaction
viscosity
oxidative coupling
phenols
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French (fr)
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Franz-Michael Dr. Bollenrath
Martin Dr. Bartmann
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Huels AG
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Chemische Werke Huels AG
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/44—Resins; Plastics; Rubber; Leather
    • G01N33/442—Resins; Plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/11—Automated chemical analysis
    • Y10T436/117497—Automated chemical analysis with a continuously flowing sample or carrier stream
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/20—Oxygen containing
    • Y10T436/200833—Carbonyl, ether, aldehyde or ketone containing

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  • the invention relates to a method to easily determine the J value of polyphenylene ethers (PPE) during the oxidative coupling reaction.
  • the J value is a measure of the molecular weight of the polymer.
  • a method for determining the viscosity of PPE during the oxidative coupling reaction is known from EP-PS 0 144 106.
  • This method consists in taking samples discontinuously from the reactor and stopping the polymerization by adding a liquid. As soon as a clear and homogeneous solution has been obtained, the throughput time of the solution can be measured through a capillary tube viscometer and the viscosity and the molecular weight can be determined from comparison with standard values. It is disadvantageous that this method can basically only be carried out batchwise. During the rapid increase in viscosity in the crucial final phase of the oxidative coupling, one is unable to state the instantaneous J value of the reaction solution.
  • This method consists in flowing a solution from the PPE reactor at a defined temperature through the preferably thermostatted Couette viscometer lets, measures the viscosity and determines the J-value with the help of a calibration curve or in some other way. The solution can then be returned to the reactor. If necessary, the viscometer must be rinsed with the solvent after each production batch.
  • the present method is bound to a certain solvent and to a certain concentration of the polymer in the solvent.
  • concentrations and solvents that deviate from the standard.
  • the described method makes it possible, in particular, to measure the viscosity directly in the existing solutions and thus to determine the instantaneous J value.
  • the time delay with which the measurement takes place is around 10 seconds and depends on the mean flow rate and the length of the inlet section to the rheometer. It is advantageously ensured that this inlet section is very short.
  • reaction solution is removed from the reactor.
  • the removal is preferably carried out continuously.
  • the viscosity measurement must be carried out at a known temperature. It is preferably a constant temperature which is in the range of the reaction temperature. It is therefore advisable to thermostate the solution removed from the reactor in a heat exchanger and to let it flow at this temperature through the Couette viscometer, which is also set to this temperature.
  • the structure of a Couette viscometer can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume 5, page 765 ff. (1980).
  • the reaction solution is then returned to the reactor.
  • the viscosity is therefore preferably measured in a viscometer through which the liquid flows in the bypass.
  • the flow rate is adjusted in a known manner by a person skilled in the art so that the axial flow through the rheometer does not significantly influence the viscosity measurement.
  • the J value can be determined from the viscosity value using a previously recorded calibration curve. In principle, it is also possible to determine the J value in a different way, for example using a mathematical approximation formula.
  • Oxygen is continuously fed to a thermostabilized reactor 1 equipped with a stirrer, which is filled to approx. 90% with reaction solution (cf. Example 2 of DE-OS 33 13 864).
  • a partial stream is removed from the reactor and fed to a measuring device 9 via a circuit 7.
  • the immersion system 6 is used for pressure control.
  • the progress of polycondensation is measured using the Circuit 10, which consists of a pump 3, a heat exchanger 4 and a Couette rheometer 5.
  • the rheometer continuously measures the viscosity of the solution. The viscosity curve is shown in FIG. 2 shown. After 74 minutes, when the desired J value of 58 is reached, which corresponds to 42 scale parts (Skt) of the display of the rheometer, the reaction is stopped by adding an excess of 50% acetic acid.

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  • General Physics & Mathematics (AREA)
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Abstract

Die Erfindung betrifft ein Verfahren zur kontinuierlichen und schnellen Bestimmung des J-Wertes bei der oxidativen Kupplungsreaktion von Phenolen zu Polyphenylenethern, wobei man dem Reaktionsansatz Lö­sung einer definierten Temperatur entnimmt, die Viskosität in einem Couette-Viskosimeter mißt und den J-Wert mit Hilfe einer Eichkurve oder auf sonstige Weise bestimmt.

Figure imgaf001
The invention relates to a method for the continuous and rapid determination of the J value in the oxidative coupling reaction of phenols to polyphenylene ethers, solution of a defined temperature being removed from the reaction mixture, the viscosity being measured in a Couette viscometer and the J value using a calibration curve or otherwise determined.
Figure imgaf001

Description

Die Erfindung betrifft ein Verfahren, um auf einfache Weise den J-Wert von Polyphenylenethern (PPE) während der oxidativen Kupplungsreaktion zu bestimmen. Der J-Wert stellt ein Maß für das Molekulargewicht des Polymeren dar.The invention relates to a method to easily determine the J value of polyphenylene ethers (PPE) during the oxidative coupling reaction. The J value is a measure of the molecular weight of the polymer.

Bekanntlich verändert sich der J-Wert zu Beginn der oxidativen Kupp­lungsreaktion nur wenig. Erst im letzten Drittel des Reaktionsab­laufes steigt der J-Wert exponentiell an. In der Praxis ist man daran interessiert, ein PPE mit möglichst konstantem Molekulargewicht her­zustellen. Gewünscht sind ferner PPE mit einem bestimmten J-Wert,da PPE mit niedrigerem oder höherem J-Wert anwendungstechnische Nach­teile haben.As is well known, the J value changes only slightly at the beginning of the oxidative coupling reaction. Only in the last third of the course of the reaction does the J-value increase exponentially. In practice, one is interested in producing a PPE with a molecular weight that is as constant as possible. PPE with a certain J-value are also desirable, since PPE with a lower or higher J-value have disadvantages in application technology.

Dies setzt voraus, den J-Wert bei der oxidativen Kupplungsreaktion mit hinreichender Genauigkeit und Schnelligkeit zu bestimmen, um die Reaktion zum gewünschten Zeitpunkt abstoppen zu können. In der Praxis bereitet dies jedoch Probleme.This requires determining the J value in the oxidative coupling reaction with sufficient accuracy and speed to be able to stop the reaction at the desired point in time. In practice, however, this creates problems.

Mißt man die zu- und abgeführte Sauerstoffmenge, was mit hinreichen­der Genauigkeit prinzipiell nur mit Schwierigkeiten möglich wäre, so ist zu berücksichtigen, daß diese nur ein sehr unzureichendes Maß für den Reaktionsablauf darstellt. Spektroskopische Verfolgungen des Reaktionsverlaufes scheiden aus, da in Lösungen gearbeitet wird, die Katalysatoren und stark gefärbte Verunreinigungen enthalten. Um eine gezielte Abstoppung der PPE-Polykondensation durchzuführen, ist es erforderlich, die Messung innerhalb von weniger als einer Minute abschließen zu können.If one measures the amount of oxygen supplied and removed, which would in principle only be possible with difficulty with sufficient accuracy, it must be taken into account that this represents only a very inadequate measure of the course of the reaction. Spectroscopic monitoring of the course of the reaction is ruled out, since work is carried out in solutions which contain catalysts and strongly colored impurities. In order to specifically stop the PPE polycondensation, it is necessary to be able to complete the measurement within less than a minute.

Im Prinzip ist es bekannt, Viskosimeter zur Messung des J-Wertes von Polymerlösungen einzusetzen. Die DIN 53 728 sieht vor, daß man das Lösemittel abdampft, eine definierte verdünnte Lösung herstellt und sodann die Viskosität in einem Ubbelohde-Viskosimeter nach DIN 51 562 bestimmt. Ein solches Verfahren ist zeitlich sehr aufwendig und daher im vorliegenden Fall nicht geeignet. Es ist auch bekannt, Viskosi­meter im Durchlauf zu betreiben und sie zur Verfolgung von Prozessen in chemischen Anlagen einzusetzen. Doch erscheint es aus folgenden Gründen als problematisch, diese Geräte bei der oxidativen Kupplungs­reaktion von Phenolen einzusetzen:

  • 1. Zu Beginn der Reaktion ist die Viskosität der Reaktionslösung außergewöhnlich niedrig; sie beträgt nur 1 - 6 mPa s und läßt sich mit den üblichen Geräten gar nicht erfassen.
  • 2. Eine Reihe von Viskosimetern erlaubt lediglich die Messung speziell vorbereiteter Proben.
  • 3. PPE scheiden sich stets in geringfügigem Maße an der Wand des Meß­instrumentes ab und beeinflussen damit die Messungen erheblich. Rohrrheometer sind daher grundsätzlich ungeeignet.
In principle, it is known to use viscometers to measure the J value of polymer solutions. DIN 53 728 provides that the solvent is evaporated off, a defined dilute solution is prepared and then the viscosity was determined in an Ubbelohde viscometer in accordance with DIN 51 562. Such a method is very time-consuming and therefore not suitable in the present case. It is also known to run viscometers continuously and to use them to monitor processes in chemical plants. However, it appears problematic to use these devices in the oxidative coupling reaction of phenols for the following reasons:
  • 1. At the beginning of the reaction, the viscosity of the reaction solution is extremely low; it is only 1 - 6 mPa s and cannot be recorded with the usual devices.
  • 2. A series of viscometers only allows the measurement of specially prepared samples.
  • 3. PPE always deposit to a small extent on the wall of the measuring instrument and thus influence the measurements considerably. Tube rheometers are therefore generally unsuitable.

Ein Verfahren zur Bestimmung der Viskosität von PPE während der oxi­dativen Kupplungsreaktion ist aus der EP-PS 0 144 106 bekannt. Dieses Verfahren besteht darin, daß man dem Reaktor diskontinuierlich Proben entnimmt und durch Zugabe einer Flüssigkeit die Polymerisation ab­stoppt. Sobald man eine klare und homogene Lösung erhalten hat, kann die Durchlaufzeit der Lösung durch ein Kapillarrohrviskosimeter ge­messen und aus dem Vergleich mit Standardwerten die Viskosität und daraus das Molekulargewicht ermittelt werden. Nachteilig ist, daß diese Methode grundsätzlich nur diskontinuierlich durchführbar ist. Während des schnellen Anstiegs der Viskosität in der entscheidenden Endphase der oxidativen Kupplung ist man nicht in der Lage, den augenblicklichen J-Wert der Reaktionslösung anzugeben.A method for determining the viscosity of PPE during the oxidative coupling reaction is known from EP-PS 0 144 106. This method consists in taking samples discontinuously from the reactor and stopping the polymerization by adding a liquid. As soon as a clear and homogeneous solution has been obtained, the throughput time of the solution can be measured through a capillary tube viscometer and the viscosity and the molecular weight can be determined from comparison with standard values. It is disadvantageous that this method can basically only be carried out batchwise. During the rapid increase in viscosity in the crucial final phase of the oxidative coupling, one is unable to state the instantaneous J value of the reaction solution.

Es wurde jetzt ein Verfahren gefunden, mit dem sich die geschilderten Nachteile vermeiden lassen. Dieses Verfahren besteht darin, daß man eine Lösung aus dem PPE-Reaktor mit einer definierten Temperatur durch das vorzugsweise thermostatisierte Couette-Viskosimeter fließen läßt, die Viskosität mißt und mit Hilfe einer Eichkurve oder auf son­stige Weise den J-Wert bestimmt. Anschließend kann die Lösung wieder in den Reaktor zurückgeführt werden. Gegebenenfall ist das Viskosi­meter nach jedem Produktionsansatz mit dem Lösemittel zu spülen.A method has now been found with which the disadvantages described can be avoided. This method consists in flowing a solution from the PPE reactor at a defined temperature through the preferably thermostatted Couette viscometer lets, measures the viscosity and determines the J-value with the help of a calibration curve or in some other way. The solution can then be returned to the reactor. If necessary, the viscometer must be rinsed with the solvent after each production batch.

Obwohl die beschriebene Methode nicht der DIN 53 728 entspricht, hat sie sich überraschenderweise als recht praktikabel erwiesen.Although the method described does not correspond to DIN 53 728, it has surprisingly proven to be quite practical.

Zwar liefert das Verfahren zu Beginn der Polykondensation nur grobe Werte, in dem entscheidenden Bereich höherer J-Werte von etwa 14 bis 30 m Pa s ist das Verfahren jedoch sehr genau. Es wurde festge­stellt, daß die Zeit bis zum Beginn des exponentiellen Viskositäts­anstieges in einem Zusammenhang mit dem erreichbaren J-Wert steht.Although the process only provides rough values at the beginning of the polycondensation, the process is very precise in the decisive range of higher J values of approximately 14 to 30 m Pa s. It was found that the time until the start of the exponential increase in viscosity is related to the achievable J value.

Im Prinzip ist das vorliegende Verfahren an ein bestimmtes Lösemittel und an eine bestimmte Konzentration des Polymeren im Lösemittel ge­bunden. Mit Hilfe mathematischer Beziehungen oder auch auf empirischen Wege durch Aufnahme von Eichkurven ist es möglich, auch bei vom Stan­dard abweichenden Konzentrationen und Lösemitteln zu arbeiten.In principle, the present method is bound to a certain solvent and to a certain concentration of the polymer in the solvent. With the help of mathematical relationships or empirically by recording calibration curves, it is also possible to work with concentrations and solvents that deviate from the standard.

Das beschriebene Verfahren ermöglicht es insbesondere, in den vor­handenen Lösungen unmittelbar die Viskosität zu messen und damit den momentanen J-Wert zu bestimmen. Die zeitliche Verzögerung, mit der die Messung erfolgt, liegt bei etwa 10 Sekunden und hängt von der mittleren Fließgeschwindigkeit und der Länge der Zulaufstrecke zum Rheometer ab. Vorteilhafterweise sorgt man dafür, daß diese Zulauf­strecke sehr kurz ist.The described method makes it possible, in particular, to measure the viscosity directly in the existing solutions and thus to determine the instantaneous J value. The time delay with which the measurement takes place is around 10 seconds and depends on the mean flow rate and the length of the inlet section to the rheometer. It is advantageously ensured that this inlet section is very short.

Im folgenden wird die Durchführung des Verfahrens näher beschrieben:The implementation of the method is described in more detail below:

Die oxidative Kupplungsreaktion von diorthosubstituierten und be­stimmten sterisch gehinderten monoorthosubstituierten Phenolen zu Polyphenylenethern wird ausführlich in den DE-OSS 32 24 692, 32 24 691 und 33 13 864 sowie den darin aufgeführten Literaturstellen beschrieben.The oxidative coupling reaction of diorthosubstituted and certain sterically hindered monoorthosubstituted phenols to polyphenylene ethers is described in detail in DE-OSS 32 24 692, 32 24 691 and 33 13 864 and the literature references listed therein.

Mit Beginn der Reaktion wird dem Reaktor Reaktionslösung entnommen. Vorzugsweise erfolgt die Entnahme kontinuierlich. Zwar ist es zu Be­ginn der Reaktion auch möglich, in kurzzeitigen Intervallen die Reak­tionslösung zu entnehmen, aber gegen Ende der Reaktion verändert sich der J-Wert so schnell, daß es zur gezielten Abstoppung der Reaktion erforderlich ist, kontinuierlich die Reaktionslösung zu entnehmen und die Viskosität zu verfolgen. Die Messung der Viskosität muß bei einer bekannten Temperatur durchgeführt werden. Vorzugsweise handelt es sich um eine konstante Temperatur, die im Bereich der Reaktionstempe­ratur liegt. Es bietet sich daher an, die dem Reaktor entnommene Lö­sung in einem Wärmeaustauscher zu thermostatisieren und mit dieser Temperatur durch das Couette-Viskosimeter fließen zu lassen, das ebenfalls auf diese Temperatur eingestellt ist. Der Aufbau eines Couette-Viskosimeters ist beispielsweise Ullmanns Encyklopädie der technischen Chemie Band 5, Seite 765 ff. (1980) zu entnehmen.At the start of the reaction, reaction solution is removed from the reactor. The removal is preferably carried out continuously. At the beginning of the reaction it is also possible to remove the reaction solution at short intervals, but towards the end of the reaction the J value changes so quickly that it is necessary to stop the reaction in a targeted manner to continuously remove the reaction solution and the viscosity to pursue. The viscosity measurement must be carried out at a known temperature. It is preferably a constant temperature which is in the range of the reaction temperature. It is therefore advisable to thermostate the solution removed from the reactor in a heat exchanger and to let it flow at this temperature through the Couette viscometer, which is also set to this temperature. The structure of a Couette viscometer can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume 5, page 765 ff. (1980).

Die Reaktionslösung wird sodann in den Reaktor zurückgeführt. Vor­zugsweise erfolgt also die Messung der Viskosität in einem Viskosi­meter, das von der Flüssigkeit im by-pass durchflossen wird. Die Strömungsgeschwindigkeit wird in bekannter Weise vom Fachmann so eingestellt, daß die axiale Durchströmung durch das Rheometer die Viskositätsmessung nicht wesentlich beeinflußt. Aus dem Viskositäts­wert läßt sich mit Hilfe einer zuvor aufgenommenen Eichkurve der J-Wert bestimmen. Prinzipiell ist es auch möglich, den J-Wert auf andere Weise zu bestimmen, beispielweise mit Hilfe einer mathema­tischen Näherungsformel.The reaction solution is then returned to the reactor. The viscosity is therefore preferably measured in a viscometer through which the liquid flows in the bypass. The flow rate is adjusted in a known manner by a person skilled in the art so that the axial flow through the rheometer does not significantly influence the viscosity measurement. The J value can be determined from the viscosity value using a previously recorded calibration curve. In principle, it is also possible to determine the J value in a different way, for example using a mathematical approximation formula.

Beispiel: (Figur 1) Example: (Figure 1)

Einem mit einem Rührwerk ausgestatteten thermostabilisierten Reaktor 1, der zu ca. 90 % mit Reaktionslösung gefüllt ist, wird kontinuier­lich Sauerstoff zugeführt (vgl. Beispiel 2 der DE-OS 33 13 864). Zur Kontrolle des O₂-Gehaltes des Gases im Reaktoreingang wird ein Teil­strom dem Reaktor entnommen und über einen Kreislauf 7 einem Meßgerät 9 zugeführt. Das Abtauchungssystem 6 dient der Druckkontrolle. Die Messung des Fortschrittes der Polykondensation erfolgt mit Hilfe des Kreislaufes 10, der aus einer Pumpe 3, einem Wärmetauscher 4 und einem Couette-Rheometer 5 besteht. Das Rheometer mißt kontinuierlich die Viskosität der Lösung. Der Viskositätsverlauf ist in FIG. 2 dar­gestellt. Nach 74 Minuten, als der angestrebte J-Wert von 58 erreicht ist, der 42 Skalenteilen (Skt) der Anzeige des Rheometers entspricht, wird die Reaktion durch Zugabe eines Überschusses 50 %iger Essigsäure abgestoppt.Oxygen is continuously fed to a thermostabilized reactor 1 equipped with a stirrer, which is filled to approx. 90% with reaction solution (cf. Example 2 of DE-OS 33 13 864). To check the O₂ content of the gas in the reactor inlet, a partial stream is removed from the reactor and fed to a measuring device 9 via a circuit 7. The immersion system 6 is used for pressure control. The progress of polycondensation is measured using the Circuit 10, which consists of a pump 3, a heat exchanger 4 and a Couette rheometer 5. The rheometer continuously measures the viscosity of the solution. The viscosity curve is shown in FIG. 2 shown. After 74 minutes, when the desired J value of 58 is reached, which corresponds to 42 scale parts (Skt) of the display of the rheometer, the reaction is stopped by adding an excess of 50% acetic acid.

Claims (2)

1. Verfahren zur kontinuierlichen und schnellen Bestimmung des J-Wertes bei der oxidativen Kupplungsreaktion von Phenolen zu Polyphenylenethern,
dadurch gekennzeichnet,
daß man dem Ansatz während der Reaktion Reaktionslösung einer bekannten Temperatur entnimmt, in einem Couette-Viskosimeter die Viskosität dieser Lösung mißt und mit Hilfe einer Eichkurve oder auf sonstige Weise den J-Wert bestimmt.1. Method for the continuous and rapid determination of the J value in the oxidative coupling reaction of phenols to polyphenylene ethers,
characterized,
that a reaction temperature of a known temperature is taken from the batch during the reaction, the viscosity of this solution is measured in a Couette viscometer and the J value is determined using a calibration curve or in some other way. 2. Verfahren gemäß Anspruch 1,
dadurch gekennzeichnet,
daß man dem Reaktionsansatz kontinuierlich in einem by-pass Reaktionslösung entnimmt, die Temperatur thermostatisiert, in einem Couette-Viskosimeter die Viskosität mißt und den J-Wert daraus bestimmt.2. The method according to claim 1,
characterized,
that one continuously removes the reaction batch in a by-pass reaction solution, thermostats the temperature, measures the viscosity in a Couette viscometer and determines the J value therefrom.
EP87102799A 1986-05-02 1987-02-27 Method for determining the J-value in the oxidative coupling reaction of phenols to polyphenylene ethers Withdrawn EP0245596A1 (en)

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DE19863614995 DE3614995A1 (en) 1986-05-02 1986-05-02 METHOD FOR DETERMINING THE J VALUE IN THE OXIDATIVE COUPLING REACTION FROM PHENOLES TO POLYPHENYLENE ETHERS

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US3347089A (en) * 1964-11-09 1967-10-17 Charles C Perry Continuous in-line viscometer
GB1197476A (en) * 1967-10-27 1970-07-08 British Petroleum Co Improvements in or Relating to Viscometers
AU416045B2 (en) * 1967-01-23 1971-08-03 Texaco Development Corporation Consistometer
DE2314671B1 (en) * 1973-03-23 1974-02-14 Rumpf Hans Prof Dr Ing METHOD AND DEVICE FOR THE INVESTIGATION OF THE STRUCTURAL CHANGES AND FOR THE MEASUREMENT OF THE STATIONARY FLOW PROPERTIES OF HIGHLY TOUGH LIQUIDS AT HIGH SHEAR
GB2123966A (en) * 1982-07-22 1984-02-08 Rheometrics Inc Apparatus for measuring viscosity and elasticity of a fluid
EP0122394A2 (en) * 1983-04-16 1984-10-24 Hüls Aktiengesellschaft Process for the preparation of polyphenylene oxides
EP0144106A1 (en) * 1983-12-05 1985-06-12 ENICHEM S.p.A. Improved process for the production of polyphenyleneoxide

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US3478111A (en) * 1967-09-25 1969-11-11 Continental Oil Co Method and apparatus for continuously monitoring the progress of certain reactions

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US3347089A (en) * 1964-11-09 1967-10-17 Charles C Perry Continuous in-line viscometer
AU416045B2 (en) * 1967-01-23 1971-08-03 Texaco Development Corporation Consistometer
GB1197476A (en) * 1967-10-27 1970-07-08 British Petroleum Co Improvements in or Relating to Viscometers
DE2314671B1 (en) * 1973-03-23 1974-02-14 Rumpf Hans Prof Dr Ing METHOD AND DEVICE FOR THE INVESTIGATION OF THE STRUCTURAL CHANGES AND FOR THE MEASUREMENT OF THE STATIONARY FLOW PROPERTIES OF HIGHLY TOUGH LIQUIDS AT HIGH SHEAR
GB2123966A (en) * 1982-07-22 1984-02-08 Rheometrics Inc Apparatus for measuring viscosity and elasticity of a fluid
EP0122394A2 (en) * 1983-04-16 1984-10-24 Hüls Aktiengesellschaft Process for the preparation of polyphenylene oxides
EP0144106A1 (en) * 1983-12-05 1985-06-12 ENICHEM S.p.A. Improved process for the production of polyphenyleneoxide

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Title
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